A Gadolinium Spin Label with Both a Narrow Central Transition and Short Tether for Use in Double Electron Electron Resonance Distance Measurements

Anokhi Shah; Amandine Roux; Matthieu Starck; Jackie A. Mosely; Michael Stevens; David G. Norman; Robert I. Hunter; Hassane El Mkami; Graham M. Smith; David Parker; Janet E. Lovett

doi:10.1021/acs.inorgchem.8b02892

A Gadolinium Spin Label with Both a Narrow Central Transition and Short Tether for Use in Double Electron Electron Resonance Distance Measurements

Anokhi Shah
, Amandine Roux
, Matthieu Starck
, Jackie A. Mosely
, Michael Stevens
, David G. Norman
, Robert I. Hunter
, Hassane El Mkami
, Graham M. Smith
, David Parker
, Janet E. Lovett

Centre for Biodiscovery

Research output: Contribution to journal › Article › peer-review

9 Citations (Scopus)

Abstract

The design, synthesis, and application of a nine-coordinate gadolinium(III)-containing spin label, [Gd.sTPATCN]-SL, for use in nanometer-distance measurement experiments by EPR spectroscopy is presented. The spin label links to cysteines via a short thioether tether and has a narrow central transition indicative of small zero-field splitting (ZFS). A protein homodimer, TRIM25cc, was selectively labeled with [Gd.sTPATCN]-SL (70%) and a nitroxide (30%) under mild conditions and measured using the double electron electron resonance (DEER) technique with both commercial Q-band and home-built W-band spectrometers. The label shows great promise for increasing the sensitivity of DEER measurements through both its favorable relaxation parameters and the large DEER modulation depth at both Q- and W-band for the inter-Gd(III) DEER measurement which, at 9%, is the largest recorded under these conditions.

Original language	English
Pages (from-to)	3015-3025
Number of pages	11
Journal	Inorganic Chemistry
Volume	58
Issue number	5
DOIs	https://doi.org/10.1021/acs.inorgchem.8b02892
Publication status	Published - 4 Mar 2019

Bibliographical note

Funding Information:
The authors thank the ERC (266804), EPSRC (EP/R013705/ 1, EP/M508214/1), and the Carnegie Trust (RIG007510) for financial support, the Wellcome Trust for a Multi-User Equipment Grant (099149/Z/12/Z), and the Royal Society for a University Research Fellowship to JEL. We also thank Professor Catherine Botting and Dr. Sally Shirran for assistance with MALDI TOF at St Andrews.

Publisher Copyright:
© 2019 American Chemical Society.

Copyright:
Copyright 2019 Elsevier B.V., All rights reserved.

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10.1021/acs.inorgchem.8b02892

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Shah, A., Roux, A., Starck, M., Mosely, J. A., Stevens, M., Norman, D. G., Hunter, R. I., El Mkami, H., Smith, G. M., Parker, D., & Lovett, J. E. (2019). A Gadolinium Spin Label with Both a Narrow Central Transition and Short Tether for Use in Double Electron Electron Resonance Distance Measurements. Inorganic Chemistry, 58(5), 3015-3025. https://doi.org/10.1021/acs.inorgchem.8b02892

@article{5c78f34d754143c1a3735a930bd38213,

title = "A Gadolinium Spin Label with Both a Narrow Central Transition and Short Tether for Use in Double Electron Electron Resonance Distance Measurements",

abstract = "The design, synthesis, and application of a nine-coordinate gadolinium(III)-containing spin label, [Gd.sTPATCN]-SL, for use in nanometer-distance measurement experiments by EPR spectroscopy is presented. The spin label links to cysteines via a short thioether tether and has a narrow central transition indicative of small zero-field splitting (ZFS). A protein homodimer, TRIM25cc, was selectively labeled with [Gd.sTPATCN]-SL (70\%) and a nitroxide (30\%) under mild conditions and measured using the double electron electron resonance (DEER) technique with both commercial Q-band and home-built W-band spectrometers. The label shows great promise for increasing the sensitivity of DEER measurements through both its favorable relaxation parameters and the large DEER modulation depth at both Q- and W-band for the inter-Gd(III) DEER measurement which, at 9\%, is the largest recorded under these conditions.",

author = "Anokhi Shah and Amandine Roux and Matthieu Starck and Mosely, \{Jackie A.\} and Michael Stevens and Norman, \{David G.\} and Hunter, \{Robert I.\} and \{El Mkami\}, Hassane and Smith, \{Graham M.\} and David Parker and Lovett, \{Janet E.\}",

note = "Funding Information: The authors thank the ERC (266804), EPSRC (EP/R013705/ 1, EP/M508214/1), and the Carnegie Trust (RIG007510) for financial support, the Wellcome Trust for a Multi-User Equipment Grant (099149/Z/12/Z), and the Royal Society for a University Research Fellowship to JEL. We also thank Professor Catherine Botting and Dr. Sally Shirran for assistance with MALDI TOF at St Andrews. Publisher Copyright: {\textcopyright} 2019 American Chemical Society. Copyright: Copyright 2019 Elsevier B.V., All rights reserved.",

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doi = "10.1021/acs.inorgchem.8b02892",

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Shah, A, Roux, A, Starck, M, Mosely, JA, Stevens, M, Norman, DG, Hunter, RI, El Mkami, H, Smith, GM, Parker, D & Lovett, JE 2019, 'A Gadolinium Spin Label with Both a Narrow Central Transition and Short Tether for Use in Double Electron Electron Resonance Distance Measurements', Inorganic Chemistry, vol. 58, no. 5, pp. 3015-3025. https://doi.org/10.1021/acs.inorgchem.8b02892

TY - JOUR

T1 - A Gadolinium Spin Label with Both a Narrow Central Transition and Short Tether for Use in Double Electron Electron Resonance Distance Measurements

AU - Shah, Anokhi

AU - Roux, Amandine

AU - Starck, Matthieu

AU - Mosely, Jackie A.

AU - Stevens, Michael

AU - Norman, David G.

AU - Hunter, Robert I.

AU - El Mkami, Hassane

AU - Smith, Graham M.

AU - Parker, David

AU - Lovett, Janet E.

N1 - Funding Information: The authors thank the ERC (266804), EPSRC (EP/R013705/ 1, EP/M508214/1), and the Carnegie Trust (RIG007510) for financial support, the Wellcome Trust for a Multi-User Equipment Grant (099149/Z/12/Z), and the Royal Society for a University Research Fellowship to JEL. We also thank Professor Catherine Botting and Dr. Sally Shirran for assistance with MALDI TOF at St Andrews. Publisher Copyright: © 2019 American Chemical Society. Copyright: Copyright 2019 Elsevier B.V., All rights reserved.

PY - 2019/3/4

Y1 - 2019/3/4

N2 - The design, synthesis, and application of a nine-coordinate gadolinium(III)-containing spin label, [Gd.sTPATCN]-SL, for use in nanometer-distance measurement experiments by EPR spectroscopy is presented. The spin label links to cysteines via a short thioether tether and has a narrow central transition indicative of small zero-field splitting (ZFS). A protein homodimer, TRIM25cc, was selectively labeled with [Gd.sTPATCN]-SL (70%) and a nitroxide (30%) under mild conditions and measured using the double electron electron resonance (DEER) technique with both commercial Q-band and home-built W-band spectrometers. The label shows great promise for increasing the sensitivity of DEER measurements through both its favorable relaxation parameters and the large DEER modulation depth at both Q- and W-band for the inter-Gd(III) DEER measurement which, at 9%, is the largest recorded under these conditions.

AB - The design, synthesis, and application of a nine-coordinate gadolinium(III)-containing spin label, [Gd.sTPATCN]-SL, for use in nanometer-distance measurement experiments by EPR spectroscopy is presented. The spin label links to cysteines via a short thioether tether and has a narrow central transition indicative of small zero-field splitting (ZFS). A protein homodimer, TRIM25cc, was selectively labeled with [Gd.sTPATCN]-SL (70%) and a nitroxide (30%) under mild conditions and measured using the double electron electron resonance (DEER) technique with both commercial Q-band and home-built W-band spectrometers. The label shows great promise for increasing the sensitivity of DEER measurements through both its favorable relaxation parameters and the large DEER modulation depth at both Q- and W-band for the inter-Gd(III) DEER measurement which, at 9%, is the largest recorded under these conditions.

UR - https://www.scopus.com/pages/publications/85062371195

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DO - 10.1021/acs.inorgchem.8b02892

M3 - Article

C2 - 30776218

AN - SCOPUS:85062371195

SN - 0020-1669

VL - 58

SP - 3015

EP - 3025

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 5

ER -

A Gadolinium Spin Label with Both a Narrow Central Transition and Short Tether for Use in Double Electron Electron Resonance Distance Measurements

Abstract

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